MCM_22_MCM_49和MCM_56三种分子筛的合成

:2005-10-13:(1973-),,,,MCM-22MCM-49MCM-56杨柳1,张凤美2,李中柱1(1.,414012;2.,100083):MWW结构分子筛是一类新型的催化材料,具有独特的10元环孔道和12元环孔穴结构,在多种反应中表现出良好的催化活性以六亚甲基亚胺作为模板剂,合成了MCM-22MCM-49和MCM-56三种分子筛,并详细考察了不同硅源凝胶配比晶化温度和晶化时间对合成过程的影响结果表明,凝胶配比和晶化温度对分子筛物相的影响较大以硅胶粉为硅源,无论在何种晶化时间下都不能得到MCM-56,只能合成出MCM-49而以碱性硅溶胶为硅源,在较短的晶化时间内就可以得到MCM-56:MWW分子筛;催化活性;合成;硅胶粉:TQ424.25;TE624.9:A:1008-1143(2006)02-0059-05SynthesisofMCM-22,MCM-49andMCM-56zeolitesYANGLiu1,ZHANGFeng-mei2,LIZhong-zhu1(1.SinopecCatalystsChanglingCompany,Yueyang414012,China;2.SinopecResearchInstituteofPetroleumProcessing,Beijing100083,China)Abstract:MWWzeolites,withtheiruniqueframeworktopologycomprisingtwoentirelydifferentm-icroporesystems(two-dimensional10MRchanneland12MRpocket),arenovelcatalyticmaterialwithexcellentcatalyticactivity.MCM-22,MCM-49andMCM-56zeolitesweresynthesizedandinflu-encesofdifferentfactors(siliconsource,gelingredient,crystallizationtemperatureandcrystallizationtime)wereinvestigated.Theresultsindicatedthatgelingredientandcrystallizationtemperaturehadremarkableinfluenceonphaseofthezeolites.OnlyMCM-49zeolitewassynthesizedfromsilicagelpowder.NoMCM-56zeolitewassynthesizedfromsilicagelpowderatanycrystallizationtemperature.MCM-56zeolitewassynthesizedfromalkalinesilicagelpowderinshortcrystallizationtime.Keywords:MWWzeolite;synthesis;catalyticactivity;silicagelpowderCLCnumber:TQ424.25;TE624.9Documentcode:AArticleID:1008-1143(2006)02-0059-051990,MCM-22[1],,[2],(0141nm@0151nm),12(0171nm@0171nm@1182nm),0140nm@0155nm10MCM-2212,,019nm,017nm10,12[3]1997,MWWMWWPSH-3SSZ-25ERB-1ITQ-1ITQ-2MCM-36MCM-49[4]MCM-56[5]MCM-22MCM-49MCM-5620062142INDUSTRIALCATALYSISFeb.2006Vol.14No.211.11.1.1原料,,,,(HMI)1.1.2合成方法MCM-22MCM-49MCM-56,,,,,40~120h22.1MCM-22MCM-492.1.1凝胶碱度的影响n(HMI)Bn(SiO2)=013,n(H2O)Bn(SiO2)=14,150e,,111Table1InfluenceofNa+/SiO2andSiO2/Al2O3ratio¹/h¹º/hº»/h»¼/h¼20MCM-4992~116MCM-49()+MOR()68MOR92~116MOR92~116MOR92~11625MCM-4936~69MCM-49()+MOR()68MOR92~116MOR92~116MOR92~11630MCM-2268~116MCM-4968~92MOR81~130MOR68~116MCM-49140MCM-49()+MOR()11635MCM-2276~144MCM-2268~92MOR68~116MOR68~116MCM-22+MOR()11640MCM-2255~116MCM-2268~116MCM-4968~116MOR68~13350MCM-2268~116MCM-2268~116MCM-22+MOR68MOR68~136MOR116¹n(OH-)Bn(SiO2)=0.18;ºn(OH-)Bn(SiO2)=0.25;»n(OH-)Bn(SiO2)=0.3;¼n(OH-)Bn(SiO2)=0.41MWWFigure1CrystallizationrangeofMWWzeolitesn(OH-)Bn(SiO2)0.4,,(MOR);n(OH-)Bn(SiO2)=0125~013,,MOR,,MCM-49MCM-22;,(MOR)n(OH-)Bn(SiO2)0125,,MCM-49;,MCM-22,(),pH[6],2.1.2凝胶硅铝比晶化温度和晶化时间的影响,n(OH-)Bn(SiO2)=0118n(H2O)Bn(SiO2)=14n(HMI)Bn(SiO2)=013,,,260200622Table2InfluenceofSiO2/Al2O3ratio,crystallizationtemperatureandcrystallizationtime140e150e155e160e170e/h/h/h/h/h15MOR68~116MOR68~116MOR68~116MOR68~116MOR68~11620MCM-4992~116MCM-4968~116MCM-4968~116MCM-4968~116MCM-4968~11625MCM-4992MCM-4955~69MCM-4944~95MCM-4940~92MCM-4940~9230MCM-2268~116MCM-2268~116MCM-4968~117MCM-4968~116MCM-4968~11635MCM-22100MCM-22100MCM-22100MCM-22100MCM-2272~87MCM-4911138MCM-2268~116MCM-2298MCM-2298MCM-22100MCM-2272~87MCM-4911140MCM-2268~116MCM-2224~116MCM-2268~116MCM-2268~116MCM-2272~87MCM-22+4911145MCM-2268~116MCM-2236~100MCM-2262~116MCM-2268~116MCM-2268~1162,20,MWW,;20~25,MCM-49;25,140~170e,MCM-22MCM-49,MCM-49,MCM-22,MCM-49,MCM-22,MCM-22MCM-49,MCM-22,LAWTONSL[7],MCM-22MCM-49,MCM-22,MCM-49180b,,/Si)O)Al0/Si)O)Si0,MCM-49,MCM-22,MWW,MCM-49[8],158~160e50h,MWWZSM-5(MFI)ZSM-35(FER)164e,ZSM-35,180e,ZSM-35;80ZSM-122.2MCM-56MCM-492.2.1硅源的影响,,MWW,,MCM-56,n(SiO2)Bn(Al2O3)=25n(OH-)Bn(SiO2)=0118n(H2O)Bn(SiO2)=14n(HMI)Bn(SiO2)=013,,140e,68h,XRD22140eMWWFigure2MWWzeoltessynthesizedfromdifferentsiliconresourceat140eA.;B.20062:MCM-22MCM-49MCM-56612,A,XRD2H8b(101)10b(102);2215b3;2519b3,MCM-49B,XRD2H8b10b,;2215b;2519b,,[5],MCM-56,,MCM-56,MCM-49,MCM-56(3),MCM-56,3~10nm,,MCM-49MCM-56MCM-56MCM-49,MCM-49MWW,,,,,MCM-56,,,,,,,MCM-493MWWFigure3SEMimagesofthreedifferentas-synthesizedMWWzeolitesA:MCM-22(P);B:MCM-49;C:MCM-562.3,n(SiO2)Bn(Al2O3)=25n(OH-)Bn(SiO2)=0118n(H2O)Bn(SiO2)=14n(HMI)Bn(SiO2)=013,,33MCM-56MCM-49Table3CrystallinetransformationfromMCM-56toMCM-49zeolites/h¹¹/%ºº/%»»/%¼¼/%½½/%2400000340000MCM-4927.744000MCM-4926.3MCM-4929.55600MCM-4933.9MCM-4944.66800MCM-5633.0MCM-4940.0MCM-4968.6800MCM-5639.1MCM-56+MCM-4945.2MCM-4969.8MCM-4988.4920MCM-5653.5MCM-56+MCM-4956.8116MCM-5628.7MCM-5657.6MCM-4989.0¹130e;º135e;»140e;¼150e;½160e3,130e,100h,6220062135e,80hMCM-56140e,120hMCM-56150e,MWW,MCM-49,MCM-56[9],,MCM-56MWW,MCM-22MCM-49,MCM-56,4140e,MWW4MCM-56Figure4CrystallinetransformationofMCM-56zeoliteunderdifferentcrystallizationtime4,68h,MCM-56,,XRD,101102,92h,101102,2215b116h,101102,2215b,2519bMCM-56,MCM-49,MWW3MCM-22MCM-49MCM-56,,MCM-49,MCM-22;MCM-49,MCM-22,MCM-22MCM-49MCM-49MCM-56,MCM-56,MCM-49150e,MCM-56:[1]RUBINMK,CHUP.Compositionofsyntheticporouscrystallinematerial,itssynthesisanduse:US,4954325[P].1990.[2]LEONOWICZMICHAELE,LAWTONJEFFREYA,LAWTONSTEPHENL.MCM-22:Amolecularsievewithtwoindependentmultidimensionalchannelsystems[J].Sc-ience,1994,264:1910-1913.[3]CORMAA,CORELLC,etal.[J].ApplCatalA,1994,115:121-134.[4]BENNETT,MICHICHAELJ.SyntheticporouscrystallineMCM-49